CN114774988A - Electrolytic cell composite diaphragm, preparation method, alkaline electrolyzed water hydrogen production device and application - Google Patents
Electrolytic cell composite diaphragm, preparation method, alkaline electrolyzed water hydrogen production device and application Download PDFInfo
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- CN114774988A CN114774988A CN202210700990.4A CN202210700990A CN114774988A CN 114774988 A CN114774988 A CN 114774988A CN 202210700990 A CN202210700990 A CN 202210700990A CN 114774988 A CN114774988 A CN 114774988A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
Abstract
The invention belongs to the technical field of hydrogen production by water electrolysis, and discloses an electrolytic cell composite diaphragm, a preparation method, an alkaline water electrolysis hydrogen production device and application thereof, wherein naphthalene chloride is used as a solvent to carry out solution blending on an organic heat-resistant alkali-resistant high molecular polymer and a hydrophilic inorganic nonmetallic oxide, volatilize the solvent, and carry out melt spinning on the blend; carrying out double-screw melt blending on an organic heat-resistant alkali-resistant high molecular polymer and a hydrophilic inorganic non-metallic oxide according to a proportion, and carrying out melt spinning; the organic heat-resistant alkali-resistant high molecular polymer is hybridized with the hydrophilic inorganic non-metallic oxide in a composite way, and the hydrophilic inorganic non-metallic oxide is welded on the surface of the organic heat-resistant alkali-resistant high molecular polymer fiber at high temperature by taking naphthalene chloride as a solvent. The invention has the common characteristics of organic materials and inorganic materials, thereby realizing the advantages of good gas barrier property, good hydrophilicity, high temperature resistance, concentrated alkali resistance, solvent resistance, low energy consumption, low price and the like, and meeting various harsh requirements of the fields related to the hydrogen production by alkaline electrolyzed water.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by electrolyzing water, and particularly relates to an electrolytic cell composite diaphragm, a preparation method, an alkaline electrolyzed water hydrogen production device and application.
Background
At present, hydrogen energy is considered as one of the major strategic directions of energy and power transformation in the world, is concerned by all countries in the world, and is considered as a necessary way for realizing carbon peak reaching and carbon neutralization. At present, the main source of hydrogen is natural gas, coal and other fossil fuels, and a large amount of carbon dioxide is still discharged in the production process. The hydrogen produced by water electrolysis is regarded as "green hydrogen" and is considered as the final direction of hydrogen production, and in water electrolysis hydrogen production, alkaline water electrolysis technology is the most mature technical route at present. Generally, a separation membrane is provided in an alkaline electrolytic water electrolysis cell to prevent mutual diffusion of hydrogen and oxygen while allowing permeation of hydroxide ions and water. Originally, asbestos was widely used due to its porous nature, but it was gradually replaced by other materials because of its poor high temperature, alkaline corrosion resistance, poor gas barrier properties, risk of explosion, and harm to the respiratory tract. Subsequently, researchers find that polymer organic membranes have high thermal stability and corrosion resistance, but have poor hydrophilicity, and the performance of directly applying the polymer organic membranes to alkaline electrolyzed water is poor, and generally composite organic membranes with good hydrophilicity are adopted to improve the performance. The melt spinning method has the advantages that: (1) the method does not need to introduce a volatile organic solvent or a post-treatment process, is green and environment-friendly, and simplifies the preparation process flow; (2) unnecessary impurities are avoided from being introduced, so that the preparation of pure fiber materials is facilitated; (3) for certain difficult to dissolve polymers such as polyphenylene sulfide, melt spinning is a necessary option. Polyphenylene Sulfide (PPS) has the characteristics of high hardness, high corrosion resistance and high glass transition temperature, and is widely applied to diaphragms. But the development of hydrogen production by water electrolysis is severely restricted by the defects of poor gas barrier property, high resistance, large energy consumption and the like.
Through the above analysis, the problems and defects of the prior art are as follows:
(1) the polymer organic membrane has poor hydrophilicity, and the performance of directly applying the polymer organic membrane to alkaline electrolyzed water is poor.
(2) The development of hydrogen production by water electrolysis is severely restricted by the defects of poor gas barrier property, high resistance, large energy consumption and the like of polyphenylene sulfide PPS.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an electrolytic cell composite diaphragm, a preparation method, an alkaline electrolyzed water hydrogen production device and application.
The invention is realized in such a way that a preparation method of the composite diaphragm of the electrolytic cell,
the composite diaphragm is formed by compounding and hybridizing an organic heat-resistant alkali-resistant high molecular polymer and a hydrophilic inorganic non-metallic oxide in different modes such as melting, solution, welding and the like, and weaving in a plain weave, a twill weave and a microgroove weave mode to obtain the organic-inorganic hybrid composite diaphragm.
Further, the solution of the melted organic heat-resistant alkali-resistant high molecular polymer and inorganic non-metal powder are blended and directly spun for composite hybridization.
Further, the temperature range of the spinning is 275-480 ℃; the fiber fineness is 0.25-20 tex; the fibers have a diameter of 100 nanometers to 100 micrometers. The spinning injection speed is 10-50 ml/min, the receiving speed is 500-1500 m/min, the relative humidity is 20-80%, and the spinning time is 0.5-5 h.
Further, the solution of the melted organic heat-resistant alkali-resistant high molecular polymer is blended with inorganic non-metal powder, and then solvent chlorinated naphthalene is volatilized and melt-spun for composite hybridization.
Further, the solution of the organic heat-resistant alkali-resistant high molecular polymer after melting and the inorganic non-metal powder double-screw are melted and blended, then are subjected to melt spinning, and are subjected to composite hybridization.
Further, the blending temperature of the solution is 20-350 ℃; the temperature of the melt spinning is 200-500 ℃.
Further, the organic heat-resistant alkali-resistant high molecular polymer is melted to obtain a solution or is melted and spun, and then the hydrophilic inorganic non-metallic oxide is welded on the surface of the organic heat-resistant alkali-resistant high molecular polymer fiber through solvent naphthalene chloride to carry out composite hybridization.
Further, the temperature of the melt blending is 100-400 ℃; the welding temperature is 20-300 ℃.
Further, the composition ratio of the organic heat-resistant alkali-resistant high molecular polymer to the hydrophilic inorganic nonmetal oxide is 0-1: 0-1.
Further, the organic heat-resistant alkali-resistant high polymer is one or a combination of more than two of polyphenylene sulfide (PPS), Polybenzimidazole (PBI), polysulfone, polyethersulfone, polyether-ether-ketone, polyimide, polyphenylene oxide, parylene, polyphenyl, aromatic polyamide, polyphenylquinoline, polypyrrole and polytetrafluoroethylene.
Further, the hydrophilic inorganic non-metallic oxide is potassium titanate K2O·xTiO2Potassium silicate K2O·xSiO2One or a combination of both; k2O·xTiO2Wherein x = 2, 4, 6, 8; k2O·xSiO2Wherein x = 2, 4, 6, 8.
Further, the preparation method of the composite diaphragm further comprises the following steps: mixing 10 g of PPS and 90 g of naphthalene chloride, and heating to 220 ℃ under mechanical stirring to dissolve for 2 hours to obtain a PPS solution; cooling to room temperature to obtain gel; and (3) crushing and extruding the gel, recovering naphthalene chloride to obtain PPS particles, drying the PPS particles in a blast oven at 120 ℃ for 12 hours to obtain PPS granules, and carrying out melt spinning. The temperature range is 300-330 ℃, and the stretching speed is 1500-3000 m/min.
Further, the preparation method of the composite diaphragm further comprises the following steps: mixing 10 g of PPS, 10 g of potassium titanate and 86 g of naphthalene chloride, and heating to 220 ℃ under mechanical stirring to dissolve for 1 hour to obtain a PPS/potassium titanate solution; cooling to room temperature to obtain gel; crushing and extruding the gel, and recovering the naphthalene chloride; and simultaneously obtaining PPS/potassium titanate particles, drying the PPS/potassium titanate particles in a forced air oven at 120 ℃ for 12 hours to obtain PPS/potassium titanate granules, and carrying out melt spinning. The temperature range is 300-330 ℃, and the stretching speed is 1500-3000 m/min, without post-treatment.
Further, the preparation method of the composite diaphragm further comprises the following steps: 10 grams of PPS/potassium titanate was mixed with 90 grams of naphthalene chloride, PPS: the weight ratio of potassium titanate is 1:1, and the potassium titanate is heated to 220 ℃ under mechanical stirring to be dissolved for 1 hour to obtain a PPS/potassium titanate solution; placing the woven PPS cloth in a solution for 10-30 seconds in a dipping and coating mode, and taking out and cooling to room temperature; and drying the PPS cloth in a blast oven at 120 ℃ for 12 hours to obtain the PPS/potassium titanate welded PPS composite diaphragm.
Further, the preparation method of the composite diaphragm further comprises the following steps: mixing 6.5 g of PBI, 6.5 g of potassium titanate and 43.5 g of DMSO, and heating to 80 ℃ under mechanical stirring to dissolve the PBI/potassium titanate to obtain a PBI/potassium titanate solution; the solution was coated onto a glass plate to give a PBI/potassium titanate film, which was dried in a forced air oven at 120 ℃ for 12 hours.
The invention also aims to provide the composite diaphragm prepared by the preparation method of the composite diaphragm, the thickness of the composite diaphragm is 0.1-2.0 mm, and the surface of the composite diaphragm is nano-porous.
Further, the thickness of the composite diaphragm is 0.8 mm-1.4 mm.
Furthermore, the aperture of the surface of the composite diaphragm is 0.1-10 nanometers.
Further, the surface of the composite diaphragm is coated with one or a combination of more than two of hydrophilic coating vinyl resin, unsaturated resin, glass flake daub, glass flake coating and epoxy resin.
The invention also aims to provide the alkaline electrolyzed water hydrogen production device which is provided with the composite diaphragm.
The invention also aims to provide application of the composite diaphragm in preparing a lithium battery.
By combining the technical scheme and the technical problem to be solved, the technical scheme to be protected by the invention has the advantages and positive effects that:
the organic-inorganic composite material is formed by combining two or more substances with different organic and inorganic phases in a physical way, and the advantages of each component are extracted to form the required structural material. The organic material and the inorganic material are compounded to make up for each other in performance, so that a synergistic effect is generated, and the comprehensive performance of the composite material is superior to that of the original composition material to meet various requirements. According to the invention, organic heat-resistant alkali-resistant high molecular polymer and hydrophilic inorganic non-metallic oxide are hybridized, compounded, spun and woven according to a specific mode to prepare the novel organic-inorganic hybrid composite diaphragm, so that the novel organic-inorganic hybrid composite diaphragm has the advantages of good gas barrier property, good hydrophilicity, high temperature resistance, concentrated alkali resistance, solvent resistance, low energy consumption, low price and the like, and can meet various harsh requirements of the field related to hydrogen production by alkaline electrolyzed water.
The invention provides a preparation method of a novel organic-inorganic hybrid composite diaphragm for hydrogen production by alkaline electrolyzed water, which makes the diaphragm draw the strong points and make up for the weak points on the basis of the common characteristics of organic materials and inorganic materials to generate a synergistic effect, thereby realizing the advantages of good gas barrier property, good hydrophilicity, high temperature resistance, concentrated alkali resistance, solvent resistance, low energy consumption, low price and the like, and meeting various harsh requirements of the relevant fields of hydrogen production by alkaline electrolyzed water.
In addition, compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a novel method for hybridization compounding, spinning and weaving of an organic heat-resistant alkali-resistant high molecular polymer and a hydrophilic inorganic non-metallic oxide.
(2) The composite diaphragm for hydrogen production by organic-inorganic hybrid alkaline electrolyzed water prepared by the invention has good gas barrier property, high hydrophilicity, high temperature resistance, concentrated alkali resistance, solvent resistance and low resistance, and meets various harsh requirements of the relevant fields of hydrogen production by alkaline electrolyzed water.
(3) The preparation process is simple and easy to produce and amplify.
(4) The melt spinning process used in the invention only needs to add a small amount of organic solvent or diluent to ensure spinnability and pore-forming property, does not need solvent recovery, and is a relatively green membrane preparation process. The melt spinning has a large draw ratio and a high productivity, and can be adjusted in a wide range.
(5) The organic heat-resistant alkali-resistant high polymer material and the hydrophilic inorganic non-metallic oxide are mixed and spun, the organic high polymer material has the characteristics of large mechanical strength, multiple varieties, designable molecules, flexibility, ultrathin property and low-cost preparation, and also has very good thermal, chemical and mechanical properties, and after being blended and spun with the hydrophilic inorganic non-metallic oxide, the organic high polymer material has strong mechanical properties, can meet various harsh requirements in the field related to hydrogen production by alkaline electrolyzed water, is also suitable for being used in extreme environments or under mechanical conditions, such as the existence of corrosive chemicals, high temperature or high mechanical tension, and has good application prospects.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a composite separator according to an embodiment of the present invention.
FIG. 2(a) shows PPS-K2O·6TiO2 And (4) microscopic images.
FIG. 2(b) shows PPS-K2O·6TiO2Microscopic view of the fibers.
FIG. 3(a) is a microscopic view of PPS.
FIG. 3(b) is a microscopic view of the material blended with the PPS and the potassium titanate solution.
FIG. 3(c) is a microscopic view of PBI film.
FIG. 3(d) is a microscopic view of a PBI and potassium titanate blended film.
FIG. 3(e) is a microscopic view of the PPS fiber.
FIG. 3(f) is a microscopic view of a film blended with PBI and potassium titanate solution.
FIG. 4 is a schematic diagram of the hydrogen production device by alkaline electrolysis of water according to the embodiment of the present invention.
Fig. 5 is a scanning electron microscope image of electrospun nanofibers provided by an embodiment of the invention.
FIG. 6 is a schematic diagram of a hybridization process provided by an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The invention combines organic heat-resistant alkali-resistant high molecular Polymer Polyphenylene Sulfide (PPS) with good high temperature resistance and chemical stability and hydrophilic inorganic non-metallic oxide potassium titanate (K)2O·xTiO2) The PPS/potassium titanate fiber is hybridized and compounded under different conditions and prepared: (1) using naphthalene chloride as a solvent to carry out solution blending on an organic heat-resistant alkali-resistant high molecular Polymer Polyphenylene Sulfide (PPS) and potassium titanate at 220 ℃, then volatilizing the solvent, and carrying out melt spinning on the blend; (2) organic heat-resistant alkali-resistant high molecular polymerPerforming double-screw melt blending on polyphenylene sulfide (PPS) and potassium titanate according to a certain proportion, and then performing melt spinning on the mixture; (3) directly using naphthalene chloride as a solvent to weld potassium titanate on the surface of the polyphenylene sulfide PPS fiber which is an organic heat-resistant alkali-resistant high molecular polymer at high temperature. The three PPS/potassium titanate fibers are woven to prepare a novel organic-inorganic hybrid composite diaphragm. The membrane has the advantages of good gas barrier property, good hydrophilicity, high temperature resistance, concentrated alkali resistance, solvent resistance, low energy consumption, low price and the like, and can meet various harsh requirements of the relevant fields of hydrogen production by alkaline electrolyzed water.
As shown in fig. 1, the preparation method of the composite membrane provided by the invention comprises the following steps:
s101: using naphthalene chloride as a solvent to carry out solution blending on an organic heat-resistant alkali-resistant high molecular polymer and potassium titanate at 220 ℃, then volatilizing the solvent, and carrying out melt spinning on the blend;
s102: carrying out double-screw melt blending on an organic heat-resistant alkali-resistant high molecular polymer and potassium titanate according to a certain proportion, and then carrying out melt spinning on the mixture;
s103: directly using naphthalene chloride as a solvent to weld potassium titanate on the surface of the organic heat-resistant alkali-resistant high-molecular polymer fiber at high temperature.
The preparation method of the composite diaphragm provided by the invention is to prepare the fiber by hybridization and compounding the organic heat-resistant alkali-resistant high molecular polymer with good high temperature resistance and chemical stability and the hydrophilic inorganic non-metallic oxide, and then prepare the novel organic-inorganic hybrid composite diaphragm by mechanical weaving.
The hybridization process provided by the embodiment of the invention is as follows: taking organic heat-resistant alkali-resistant high molecular polymer such as polyphenylene sulfide and hydrophilic inorganic non-metallic oxide such as potassium titanate as examples, the specific hybridization process is as follows: PPS was dissolved in a naphthalene chloride solvent at 220 degrees celsius, mixed with potassium titanate powder, and stirred well for 10 minutes. After cooling, the mixture is dried at 120 ℃ to constant weight. The specific process is shown in FIG. 6.
The organic heat-resistant alkali-resistant high polymer with high temperature resistance and good chemical stability is one or the combination of more than two of polyphenylene sulfide (PPS), Polybenzimidazole (PBI), polysulfone, polyethersulfone, polyetheretherketone, polyimide, polyphenylene oxide, parylene, polyphenyl, aromatic polyamide, polyphenylquinoline, polypyrrole, polytetrafluoroethylene and the like.
The hydrophilic inorganic nonmetal oxide of the present invention is potassium titanate (K)2O•xTiO2) Potassium silicate (K)2O•xTiO2) One kind or a combination of two or more kinds of them; said K2O•xTiO2Wherein x = 2, 4, 6, 8; said K2O•xTiO2Wherein x = 2, 4, 6, 8.
The method for preparing the fiber by hybridization and compounding of the organic heat-resistant alkali-resistant high molecular polymer and the hydrophilic inorganic non-metallic oxide comprises but is not limited to direct spinning after solution blending, solvent volatilization and melt spinning after solution blending, melt spinning after twin-screw melt blending, and fusion spinning of the hydrophilic inorganic non-metallic oxide on the surface of the fiber through the solvent after the solution (or melt) spinning of the organic heat-resistant alkali-resistant high molecular polymer.
The novel organic-inorganic hybrid composite diaphragm is prepared by a mechanical weaving mode.
The composite diaphragm is a compact film, the surface of the composite diaphragm is nano-porous, the hydrogen penetration blocking capacity is high, and meanwhile, the hydrophilic coating is coated on the surface of the diaphragm, so that the electrolyte permeability is high.
The aperture of the surface of the composite diaphragm is 0.1-10 nanometers; the surface of the diaphragm is coated with a hydrophilic coating, and the hydrophilic coating is one or the combination of more than two of vinyl resin, unsaturated resin, glass flake daub, glass flake coating and the like (epoxy resin).
The proportion of the organic heat-resistant alkali-resistant high molecular polymer to the hydrophilic inorganic non-metallic oxide composite hybrid is any composition ratio between 0 and 1.
The temperature range of the solution blending is 20-350 ℃; the temperature of the melt blending is 100-400 ℃; the temperature range of melt spinning is 200-500 ℃; the temperature range of the welding is 20-300 ℃.
The fibers of the present invention have diameters ranging from 100 nanometers to 100 micrometers; more preferably, the fibers have a diameter in the range of 10 microns to 50 microns.
The thickness of the mechanical weaving composite diaphragm is 0.1 mm-2.0 mm; more preferably, the membrane has a thickness in the range of 0.8 mm to 1.4 mm.
The novel organic-inorganic hybrid composite diaphragm for hydrogen production by alkaline electrolysis of water prepared by the invention has the advantages of good gas barrier property, good hydrophilicity, high temperature resistance, concentrated alkali resistance, solvent resistance, low energy consumption, low price and the like.
The technical solution of the present invention is further described with reference to the following specific examples.
Example 1: in the embodiment of the invention, 10 g of PPS and 90 g of chlorinated naphthalene are mixed, and the mixture is heated to 220 ℃ under mechanical stirring to be dissolved for 2 hours to obtain a PPS solution. When the temperature is cooled to room temperature, the system is in a gel state. And (3) crushing and extruding the gel, recovering naphthalene chloride, obtaining PPS particles at the same time, and drying in a blast oven at 120 ℃ for 12 hours to obtain PPS granules which are suitable for melt spinning.
Example 2: in the present example, 10 g of PPS and 10 g of potassium titanate (K)2O·6TiO2) Mixed with 86 g of naphthalene chloride, and heated to 220 ℃ under mechanical stirring to dissolve for 1 hour, thus obtaining a PPS/potassium titanate solution. When the temperature is cooled to room temperature, the system is in a gel state. Crushing and extruding the gel, and recovering the naphthalene chloride; and simultaneously obtaining PPS/potassium titanate particles, and drying the PPS/potassium titanate particles in a forced air oven at 120 ℃ for 12 hours to obtain PPS/potassium titanate granules which are suitable for melt spinning.
Example 3: in the example of the present invention, 10 g of PPS/potassium titanate (weight ratio: 1) was mixed with 90 g of naphthalene chloride, and the mixture was heated to 220 ℃ with mechanical stirring to dissolve the mixture for 1 hour, thereby obtaining a PPS/potassium titanate solution. And (3) placing the woven PPS cloth in the solution for 10-30 seconds in a dipping coating mode, and taking out and cooling to room temperature. And drying the PPS cloth in a blast oven at 120 ℃ for 12 hours to obtain the PPS/potassium titanate welded PPS composite diaphragm. As shown in fig. 2, PPS/potassium titanate fiber (PPS-K) according to the present invention = was provided2O·6TiO2) A microscopic view; wherein FIG. 2(a) is PPS-K2O·6TiO2 A microscopic view; FIG. 2(b) shows PPS-K2O·6TiO2Microscopic view of the fiber.
Example 4: example of the invention 6.5 grams of PBI, 6.5 grams of potassium titanate (K)2O·6TiO2) Mixed with 43.5 grams DMSO and heated to 80 degrees celsius with mechanical agitation to dissolve, resulting in a PBI/potassium titanate solution. The solution was coated onto a glass plate to give a PBI/potassium titanate film, which was dried in a forced air oven at 120 ℃ for 12 hours.
Example 5: an SEM image of the surface of the film obtained by spraying a 13% mixed solution of PBI/potassium titanate (1: 1 by weight) is shown in FIG. 3.
As can be seen from fig. 3, potassium titanate is uniformly distributed in the PBI polymer in the form of short fibers. Wherein FIG. 3(a) is PPS; FIG. 3(b) shows a material blended with PPS and a potassium titanate solution; FIG. 3(c) is a PBI film; FIG. 3(d) is a PBI and potassium titanate blend film; FIG. 3(e) is a PPS fiber; FIG. 3(f) is a film of PBI blended with potassium titanate solution.
Example 6: in the present example, 10 g of polyether sulfone (PES) and 10 g of potassium titanate (K)2O·6TiO2) Mixed with 86 g of naphthalene chloride, heated to 170 ℃ with mechanical stirring to dissolve for 1 hour to obtain a PES/potassium titanate solution. When the temperature is cooled to room temperature, the system is in a gel state. Crushing and extruding the gel, and recovering the naphthalene chloride; PES/potassium titanate solid is obtained at the same time, and is dried in a forced air oven at 120 ℃ for 12 hours to obtain PES/potassium titanate granules which are suitable for melt spinning.
Example 7: in the present example, 5 g of Polytetrafluoroethylene (PVDF) and 5 g of potassium titanate (K)2O·6TiO2) Mixed with 20 mL of N, N-dimethylformamide and dissolved at room temperature for 48 hours under mechanical stirring to obtain a PVDF/potassium titanate solution. The solution was coated onto a glass plate to obtain a PVDF/potassium titanate film, which was dried in a forced air oven at 60 ℃ for 12 hours.
Example 8: in the present example, 10 g of PPS and 5 g of potassium titanate (K)2O·6TiO2) With 5 g of potassium silicate (K)2O·6SiO2) And 86 grams of naphthalene chloride were mixed and dissolved by heating to 400 c for 0.5 hours with mechanical stirring to obtain a PPS/potassium titanate/potassium silicate solution. When the temperature is cooled to room temperature, the system is in a gel state. Crushing and extruding the gel, and recovering the naphthalene chloride; meanwhile, PPS/potassium titanate particles are obtained, and are dried in a forced air oven at 120 ℃ for 12 hours to obtain PPS/potassium titanate/potassium silicate granules which are suitable for melt spinning.
Example 9: in the present example, 5 g of Polyimide (PI), 5 g of Polytetrafluoroethylene (PVDF) and 5 g of potassium titanate (K)2O·6TiO2) 5 g of potassium silicate (K)2O·6SiO2) 20 g of N, N-Dimethylacetamide (DMAC) and 86 g of naphthalene chloride are mixed and dissolved for 4 hours by heating to 80 ℃ with mechanical stirring to obtain a solution of PI/PVDF/potassium titanate/potassium silicate. When the temperature is cooled to room temperature, the system is in a gel state. Crushing and extruding the gel, and recovering the naphthalene chloride; and PI/PVDF/potassium titanate/potassium silicate particles are obtained at the same time, the PI/PVDF/potassium titanate/potassium silicate particles are obtained and dried in a forced air oven for 10 hours at 150 ℃, PI/PVDF/potassium titanate/potassium silicate particles are obtained and stirred for 5 times under a high-speed crusher, the materials are uniformly mixed every time for 30 seconds, then melt spinning is carried out at 200 ℃, and the particles are dried at room temperature.
Example 10: in the present example, 5 g of polysulfone, 5 g of polyimide and 15 g of potassium silicate K were mixed2O·4SiO2Mixed with 50ml of N, N-dimethylacetamide, heated to 100 ℃ with mechanical stirring and stirred for 6 hours to obtain a polysulfone/polyethersulfone/potassium silicate mixed solution. And (3) standing the solution to remove bubbles, scraping the solution on a glass plate by using a film scraper to ensure uniformity and no bubbles to obtain a polysulfone/polyether sulfone/potassium silicate film, and drying the film in a forced air oven at 100 ℃ for 24 hours.
Example 11: 10 g of polysulfone, 10 g of PVDF and 15 g of potassium titanate K2O·6TiO2Mixing with 50mL of N, N-dimethylformamide, heating to 60 ℃ under mechanical stirring, stirring for 8 hours, standing the blending solvent for one night to remove bubbles to obtain a uniform mixed solution, and carrying out electrostatic spinning at room temperature for 8 hours at a distance of 15 cm. A polysulfone/PVDF/potassium titanate film is obtained which is dried at 60 ℃ for 24 hours. Observing the distribution of fibersThe difference between the conditions and the melt spun fiber. The scanning electron micrograph of the electrospun nanofibers is shown in FIG. 5 below.
Example 12: in the present example, 10 g of PPS/potassium silicate (weight ratio: 1) was mixed with 90 g of naphthalene chloride, and the mixture was dissolved by heating to 350 ℃ for 1 hour with mechanical stirring to obtain a PPS/potassium silicate solution. The woven PPS cloth is placed in the solution for 15 seconds in a dip coating mode, and is taken out and cooled to room temperature. And drying the PPS cloth in a blast oven at the temperature of 80 ℃ for 24 hours to fully volatilize the solvent to obtain the PPS/potassium silicate welded PPS composite membrane.
In order to prove the creativity and the technical value of the technical scheme of the invention, the part is the application example of the technical scheme of the claims on specific products or related technologies.
(1) The composite diaphragm prepared by the embodiment of the invention can be applied to an alkaline electrolytic water electrolyzer to prevent mutual diffusion of hydrogen and oxygen and allow penetration of hydroxide ions and water.
(2) The monofilament prepared by melt spinning has strong mechanical property, is suitable for being used in extreme environments or under mechanical conditions, such as the existence of corrosive chemicals, high temperature or high mechanical tension occasions, and can be applied to fishing lines and fishing nets.
(3) The combination of the high molecular polymer and the hydrophilic inorganic non-metal oxide has the advantages of the high molecular polymer and the hydrophilic inorganic non-metal oxide, and part of the high molecular polymer has piezoelectric property and thermoelectric property, such as PVDF. The high molecular polymer and the hydrophilic inorganic non-metallic oxide are combined and applied to the field of intelligent fabrics. Such as fitting a heart-lung monitor to a bed sheet or belt to monitor the patient's heart-lung condition, wearable sensors may be used to assist with the blind's fingertips.
(4) The fiber prepared from the high-temperature polymer is particularly suitable for filtering hot gas or corrosive fluid, and the composite membrane prepared by the method has the advantages of high hydrophilicity, high temperature resistance, concentrated alkali resistance, solvent resistance and low resistance. The cable sheath can be used for cable insulation and protective textiles, such as fire-proof clothes, airplane seat covers, stab-resistant gloves, stab-resistant clothes and other fields.
The above description is only for the purpose of illustrating the embodiments of the present invention, and the scope of the present invention should not be limited thereto, and any modifications, equivalents and improvements made by those skilled in the art within the technical scope of the present invention as disclosed in the present invention should be covered by the scope of the present invention.
Claims (16)
1. The composite diaphragm for the electrolytic cell is characterized by being obtained by carrying out composite hybridization on an organic heat-resistant alkali-resistant high molecular polymer and a hydrophilic inorganic non-metallic oxide in different modes and weaving.
2. The composite separator for electrolytic cell according to claim 1, wherein the organic heat-resistant alkali-resistant high molecular polymer is one or a combination of two or more of polyphenylene sulfide (PPS), Polybenzimidazole (PBI) polysulfone, polyethersulfone, polyetheretherketone, polyimide, polyphenylene oxide, parylene, polyphenylene, aramid, polyphenylquinoline, polypyrrole, and polytetrafluoroethylene.
3. The composite separator for electrolytic cell according to claim 1, wherein said hydrophilic inorganic non-metallic oxide is potassium titanate K2O·xTiO2Potassium silicate K2O·xSiO2One or a combination of both; k2O·xTiO2Wherein x = 2, 4, 6, 8; k2O·xSiO2Wherein x = 2, 4, 6, 8.
4. The composite separator for electrolytic cell as claimed in claim 1, wherein the composition ratio of the organic heat and alkali resistant high molecular polymer to the hydrophilic inorganic non-metallic oxide is 0-1: 0-1.
5. The composite separator for electrolytic cells according to claim 1, wherein the thickness of the composite separator is 0.1 mm to 2.0 mm, and the surface of the composite separator is nanoporous.
6. The composite separator for an electrolytic cell according to claim 1, wherein the pore diameter of the surface of the composite separator is 0.01 nm to 0.1 nm.
7. The composite separator for electrolytic cell according to claim 1, wherein the surface of said composite separator is coated with one or a combination of two or more of hydrophilic coating vinyl resin, unsaturated resin, glass flake cement, glass flake coating, and epoxy resin.
8. The preparation method of the composite diaphragm of the electrolytic cell is characterized in that the preparation method comprises the steps of carrying out composite hybridization on an organic heat-resistant alkali-resistant high molecular polymer and a hydrophilic inorganic non-metallic oxide in different modes of melting, solution blending or surface welding, and carrying out plain weave, twill weave and dense grain weave to obtain the organic-inorganic hybrid composite diaphragm.
9. The method for preparing the composite diaphragm of claim 8, wherein the solution of the organic heat-resistant alkali-resistant high molecular polymer after melting is blended with inorganic non-metal powder for direct spinning to perform composite hybridization.
10. The method for preparing the composite membrane according to claim 8, wherein the temperature range of the blending direct spinning is 275 ℃ to 480 ℃; the fiber fineness is 0.25-20 tex; the fibers have a diameter of 100 nanometers to 100 micrometers.
11. The method for preparing the composite diaphragm of claim 8, wherein the solution of the melted organic heat-resistant alkali-resistant high molecular polymer is blended with inorganic non-metal powder, and then solvent naphthalene chloride is volatilized and melt-spun to perform composite hybridization; the temperature range is 300-330 ℃, and the stretching speed is 1500-3000 m/min, without post-treatment.
12. The method for preparing the composite diaphragm of claim 8, wherein the solution of the organic heat-resistant alkali-resistant high molecular polymer after melting and the inorganic non-metal powder are subjected to melt spinning after double-screw melting and blending, and composite hybridization is performed.
13. The method for preparing the composite separator according to claim 8, wherein the organic heat-resistant alkali-resistant high molecular polymer is melted into a solution or is melted and spun, and then the hydrophilic inorganic non-metal oxide is welded on the surface of the organic heat-resistant alkali-resistant high molecular polymer fiber through naphthalene chloride serving as a solvent, so as to perform composite hybridization.
14. The method of preparing a composite separator according to claim 8, wherein the temperature of the solution blending is 20 to 350 degrees celsius; the temperature of the melt spinning is 200-500 ℃.
15. The method of making a composite separator according to claim 8, wherein the temperature of the melting, solution blending is between 100 degrees celsius and 400 degrees celsius; the temperature of the welding is 20-300 ℃.
16. An alkaline water electrolysis hydrogen production device, which is characterized in that the alkaline water electrolysis hydrogen production device is provided with the composite diaphragm of claim 1.
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| CN116988102A (en) * | 2023-07-26 | 2023-11-03 | 江苏大学 | Nano transport alkaline electrolyzed water diaphragm and manufacturing method thereof |
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